Details
| Originalsprache | Englisch |
|---|---|
| Seiten (von - bis) | 5524-5532 |
| Seitenumfang | 9 |
| Fachzeitschrift | Organic and Biomolecular Chemistry |
| Jahrgang | 16 |
| Ausgabenummer | 30 |
| Frühes Online-Datum | 20 Juli 2018 |
| Publikationsstatus | Veröffentlicht - 14 Aug. 2018 |
Abstract
The strobilurins are important antifungal metabolites isolated from a number of basidiomycetes and have been valuable leads for the development of commercially important fungicides. Isotopic labelling studies with early and advanced intermediates confirm for the first time that they are produced via a linear tetraketide, primed with the rare benzoate starter unit, itself derived from phenylalanine via cinnamate. Isolation of a novel biphenyl metabolite, pseudostrobilurin B, provides evidence for the involvement of an epoxide in the key rearrangement to form the β-methoxyacrylate moiety essential for biological activity. Formation of two bolineol related metabolites, strobilurins Y and Z, also probably involves epoxide intermediates. Time course studies indicate a likely biosynthetic pathway from strobilurin A, with the simplest non-subsubstituted benzoate ring, to strobilurin G with a complex dioxepin terpenoid-derived substituent. Precursor-directed biosynthetic studies allow production of a number of novel ring-halogenated analogues as well as a new pyridyl strobilurin. These studies also provide evidence for a non-linear biosynthetic relationship between strobilurin A and strobilurin B.
ASJC Scopus Sachgebiete
- Biochemie, Genetik und Molekularbiologie (insg.)
- Biochemie
- Chemie (insg.)
- Physikalische und Theoretische Chemie
- Chemie (insg.)
- Organische Chemie
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in: Organic and Biomolecular Chemistry, Jahrgang 16, Nr. 30, 14.08.2018, S. 5524-5532.
Publikation: Beitrag in Fachzeitschrift › Artikel › Forschung › Peer-Review
}
TY - JOUR
T1 - Investigations into the biosynthesis of the antifungal strobilurins
AU - Iqbal, Zafar
AU - Han, Li Chen
AU - Soares-Sello, Anna M.
AU - Nofiani, Risa
AU - Thormann, Gerald
AU - Zeeck, Axel
AU - Cox, Russell J.
AU - Willis, Christine L.
AU - Simpson, Thomas J.
N1 - Funding information: AMS-S thanks the Commonwealth Scholarship Commission for a postgraduate scholarship. L-CH thanks BrisSynBio, the Centre for Synthetic Biology (BB/L01386X/1) for fellowship support. RN thanks the Directorate General of Resources for Science and Higher Education (Beasiswa Pendidikan Pascasarjana Luar Negeri Direktorat Jenderal Sumber Daya Ilmu Pengetahuan dan Pendidikan Tinggi) (BPP-LN Ditjen SD Iptek-Dikti), Republic of Indonesia, for an Overseas Postgraduate Scholarship and the Alumni foundation of the University of Bristol for financial support. ZI thanks the Higher Education Commission of Pakistan for a post-graduate scholarship. RJC thanks EPSRC (EP/F066104/1) and DFG (INST 187/621-1) for LCMS equipment. GT and AZ are grateful to Prof. Tim Anke for providing us with Strobilurus tenacellus. Dr Y. O’Connell is thanked for synthesis of labelled cinnamate.
PY - 2018/8/14
Y1 - 2018/8/14
N2 - The strobilurins are important antifungal metabolites isolated from a number of basidiomycetes and have been valuable leads for the development of commercially important fungicides. Isotopic labelling studies with early and advanced intermediates confirm for the first time that they are produced via a linear tetraketide, primed with the rare benzoate starter unit, itself derived from phenylalanine via cinnamate. Isolation of a novel biphenyl metabolite, pseudostrobilurin B, provides evidence for the involvement of an epoxide in the key rearrangement to form the β-methoxyacrylate moiety essential for biological activity. Formation of two bolineol related metabolites, strobilurins Y and Z, also probably involves epoxide intermediates. Time course studies indicate a likely biosynthetic pathway from strobilurin A, with the simplest non-subsubstituted benzoate ring, to strobilurin G with a complex dioxepin terpenoid-derived substituent. Precursor-directed biosynthetic studies allow production of a number of novel ring-halogenated analogues as well as a new pyridyl strobilurin. These studies also provide evidence for a non-linear biosynthetic relationship between strobilurin A and strobilurin B.
AB - The strobilurins are important antifungal metabolites isolated from a number of basidiomycetes and have been valuable leads for the development of commercially important fungicides. Isotopic labelling studies with early and advanced intermediates confirm for the first time that they are produced via a linear tetraketide, primed with the rare benzoate starter unit, itself derived from phenylalanine via cinnamate. Isolation of a novel biphenyl metabolite, pseudostrobilurin B, provides evidence for the involvement of an epoxide in the key rearrangement to form the β-methoxyacrylate moiety essential for biological activity. Formation of two bolineol related metabolites, strobilurins Y and Z, also probably involves epoxide intermediates. Time course studies indicate a likely biosynthetic pathway from strobilurin A, with the simplest non-subsubstituted benzoate ring, to strobilurin G with a complex dioxepin terpenoid-derived substituent. Precursor-directed biosynthetic studies allow production of a number of novel ring-halogenated analogues as well as a new pyridyl strobilurin. These studies also provide evidence for a non-linear biosynthetic relationship between strobilurin A and strobilurin B.
KW - Antifungal Agents/chemistry
KW - Basidiomycota/chemistry
KW - Biosynthetic Pathways
KW - Epoxy Compounds/chemistry
KW - Fatty Acids, Unsaturated/chemistry
KW - Fungicides, Industrial/chemistry
KW - Halogenation
KW - Strobilurins/chemistry
UR - http://www.scopus.com/inward/record.url?scp=85050969386&partnerID=8YFLogxK
U2 - 10.1039/c8ob00608c
DO - 10.1039/c8ob00608c
M3 - Article
C2 - 30027987
AN - SCOPUS:85050969386
VL - 16
SP - 5524
EP - 5532
JO - Organic and Biomolecular Chemistry
JF - Organic and Biomolecular Chemistry
SN - 1477-0520
IS - 30
ER -